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#100% accuracy moves can only fail in Generation I.#

In the Generation I games, even moves with a 100% accuracy would miss once in a great while for seemingly no reason whatsoever. This was due to accuracy being internally calculated as a fraction of 256, when the highest internal accuracy a move could possess was 255 (FF in hexadecimal, and the highest value expressible in a single byte), yielding an accuracy of 99.6%. This also applied to secondary effects such as poison or paralysis, but it was resolved in Generation II.

Harvest didn't exist in Generation I, so there is no way Harvest can fail in the sun, and I doubt it would even if 100 accuracy moves could miss.